EP0069941A1 - Gewinnung von Wasserstoff aus Gasströmen mittels Metallhydriden - Google Patents

Gewinnung von Wasserstoff aus Gasströmen mittels Metallhydriden Download PDF

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Publication number
EP0069941A1
EP0069941A1 EP82105933A EP82105933A EP0069941A1 EP 0069941 A1 EP0069941 A1 EP 0069941A1 EP 82105933 A EP82105933 A EP 82105933A EP 82105933 A EP82105933 A EP 82105933A EP 0069941 A1 EP0069941 A1 EP 0069941A1
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EP
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Prior art keywords
hydrogen
ballast
desorption
composite
reactor
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EP82105933A
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English (en)
French (fr)
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EP0069941B1 (de
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John Joseph Sheridan, Iii
Fred Gary Eisenberg
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Air Products and Chemicals Inc
MPD Technology Corp
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Air Products and Chemicals Inc
MPD Technology Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0473—Rapid pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0078—Composite solid storage media, e.g. mixtures of polymers and metal hydrides, coated solid compounds or structurally heterogeneous solid compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0084—Solid storage media characterised by their shape, e.g. porous compacts or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by using hydrogen storage media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1126—Metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/65—Employing advanced heat integration, e.g. Pinch technology
    • B01D2259/655—Employing advanced heat integration, e.g. Pinch technology using heat storage materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0423—Beds in columns
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/90—Hydrogen storage

Definitions

  • This invention pertains to a process for separating hydrogen from a mixed gas stream via the utilization of a hydride.
  • the second type of hydrogen purification process utilizes a hydridable material, and such material combines chemically with hydrogen to form metallic hydrides.
  • hydrogen is the component adsorbed and the contaminants are allowed to pass through.
  • the following patents relate to hydrogen separation or storage and storage processes using a hydridable material:
  • Sandrock et al disclose an adiabatic process which uses a thermal ballast with a hydride storage material to recover the energy generated during exothermic hydriding, that energy stored in the thermal ballast.
  • the examples show using a bath of water or molten sodium sulfate decahydrate as thermal ballast to recover the heat generated during hydriding and recovering the heat from the bath to enhance desorption.
  • This invention relates to an improved adiabatic type process for separating hydrogen from a gas mixture.
  • the improvement permits one to achieve faster cycling times while using minimal energy requirements and achieving excellent bed effectiveness.
  • the improvement in an adiabatic hydrogen separation process comprises:
  • Figure 1 is a plot of idealized equilibrium curves of a hydride-forming metal, in which typical isotherms are shown with relation to the equilibrium pressure versus hydrogen capacity of the hydride-forming metal.
  • FIG. 2 is a schematic process diagram of the process apparatus used in the preferred form of the present invention.
  • FIG 1 there is shown two isothermal equilibrium curves, for the temperatures of 38°C and 100°C for a LaNi5--H2 system, wherein the log of the partial pressure (p) of hydrogen (ordinate) is plotted against bed loading capacity (c) (abscissa) namely hydrogen to metal ratio (H/M).
  • the starting point for an idealized process in accordance with the present invention by reference to Figure 1, with starting conditions of 50 psi, partial pressure hydrogen (P 1 ) initial hydrogen concentration C 1 and 38°C, (T l ) is point A, a point along the 38°C isothermal curve.
  • P 1 partial pressure hydrogen
  • T l initial hydrogen concentration C 1 and 38°C
  • P 2 partial pressure hydrogen
  • the hydridable metal mass In a partially ballasted adiabatic system the hydridable metal mass would traverse the line A - B. Thus, the final equilibrium condition realized by the reactant mass is a point further along to the higher loading end of the 100°C isotherm, namely, point B. However, the amount of ballast can be adjusted as will be disclosed so that essentially full loading can be achieved which corresponds to B" on the 100°C isotherm. In an isothermal system the path would follow the isothermal line to point C on the 38°C isothermal line.
  • the ballast material, with which the hydridable material is combined in spatially distributed manner to form a composite is an inert, small particulate material, such as metals generally of copper, nickel, aluminum or iron.
  • the ballast will have good heat conductive properties and will have a particle size approximately 1-100 times (but not in excess of 4 mesh, and preferably less than 40 mesh) that of the hydridable material after hydrogenation.
  • the particle size of the hydridable material after hydriding is from submicron to 100 mesh in diameter, and the ballast will be of similar size.
  • ballast material which is present as individual particles, randomly distributed so as to be in contact with the hydridable material; ballast material which is present as a reticulated network such as obtainable by sintering ballast material with hydridable material to form ballast-bound integral composite structures, a particularly useful form of which is that of pellets as disclosed in copending application U.S. Serial No.
  • ballast material which is present in a pellet as one or more masses such as a sphere, to which hydridable material in a thin layer is adhered; ballast material which is present in pellets as any combination of the foregoing, for example, a combination of a reticulated network and randomly distributed particles, or a combination of randomly distributed equiaxed particles and randomly distributed fine wire-like or fiber-like particles.
  • the amount of thermal ballast employed in the composite controls, in part, the amount of hydrogen removed from the feed stream.
  • Other factors include hydrogen partial pressure of the feed stream, hydridable material type, feed stream temperature and velocity, desired hydrogen recovery pressure, etc. If the quantity of thermal ballast is too small, the entire reactor mass (thermal ballast plus hydridable material) will be heated by the exothermic hydriding reaction to a temperature, T 2 , such that the hydriding reaction stops before the hydridable material is completely converted to hydride.
  • the temperature T 2 is determined by the hydrogen partial pressure in the feed stream and the pressure-temperature relationship that exists for the particular hydridable material.
  • the thermal ballast exceeds a critical amount, the energy provided by the exothermic hydriding reaction will be insufficient to heat the reactor to T 2 . In this case, the hydriding reaction will proceed rapidly to completion but the final temperature of the reactor mass will be less than the desired value T 2 . This lower temperature represents an inefficient use of the bed volume and reduced hydrogen pressures available during desorption.
  • the desired quantity of thermal ballast will result in the reactor mass rising from the initial temperature T l to the final temperature T 2 just as the hydridable material is completely hydrided, and for this condition the ratio of the weight of the thermal ballast to the weight of hydridable material is termed the theoretical ratio.
  • ballast is used in a range of 90-150% of the theoretical ratio.
  • the 50% minimum required amount of ballast material for achieving this level then is determined by ascertaining an initial temperature, calculating the heat absorbtion characteristics of the hydridable material and the ballast, ascertaining the heat released by hydriding the amount of hydridable material present ( ⁇ H), ascertaining the temperature at which the equilibrium pressure of hydrogen with respect to the hydride is equal to the partial pressure of hydrogen in the feed gas, determining a ⁇ T by difference between the initial temperature (T 1 ) and the maximum permissible temperature (T 2 ), applying the ⁇ T to a summation of the heat absorption characteristics of the materials present in the reactor and solving for the unknown quantity of ballast as in the equation below.
  • ⁇ T should be at - least 10°C and generally in a range from 20 to 80°C.
  • pellets which include the ballast material are advantageous and preferred to employ pellets which include the ballast material as the pellet binder rather than use polymeric binder. Such pellets transfer heat much more readily and permit faster absorption and desorption rates.
  • pellets are advantageously made by sintering hydridable material such as LaNi 5 with nickel or other sinterable metal powder. Sintering can be conveniently done by heating blended amounts of LaNi S and metal powder which have been pressed or otherwise formed (e.g. by extrusion and slicing) into pellets. In the case of nickel, sintering can be carried out at temperatures in the range of about 700°C to about 900°C for about 0.1 to about 2 hours.
  • pellets can be formed which consist of the hydride-forming material and ballast powder by binding with a resinous binder, such as silicone rubber in a proportion of about 0.01 to 5% by weight.
  • a resinous binder such as silicone rubber
  • This solid mixture typically is about 4 grams in weight and in the shape of a cylinder one-half inch high and a half-inch in diameter.
  • a high pressure pelletizer capable of pelletizing at 1,000 to 30,000 psi may be used.
  • the pressed pellet can be cut, such as into quarter-cylinder segments, about one-quarter inch on a side, before use.
  • the purpose of cutting the pelletized composite is to increase the surface area for hydrogen reaction and diffusion throughout the composite.
  • the cut pellets are also activated, preferably such as by exposure to high pressure hydrogen, prior to use.
  • plastic or polymeric binders inhibit heat transfer within the pellet and often this causes unacceptable reaction front lengths and reaction front velocities.
  • This short heat transfer path is ensured by providing an intimate mix of the small particle heat ballast material and hydridable metal in forming the composite preferably in the form of pellets as used in the reactor.
  • heat conduction as a heat transfer mechanism generally has been relatively inefficient due to small contact surface areas and poor heat conductivity of the binder.
  • Heat transfer by hydrogen convection is also inefficient because of tortuous gas flow passages and because of the generally low heat capacity of gases in the gas stream.
  • the conduction and convection processes are facilitated and reaction times may be made short. This is not the case, for example, with the heat ballast external to and not in contact with or in intimate mixture with the hydridable material; in this case the rates of absorption and desorption are slower.
  • the heat ballast material for example, a metal such as nickel, in the form of particles each of which is only a small fraction of the volume of the pellet. Recognizing that after a few hydriding- dehydriding cycles, the hydridable material itself will be reduced to particle sizes of a few microns, the size of the hydridable material itself used to form the pellet is not really important so long as each pellet 'contains a substantial number of hydridable metal particles, for example, at least about 10 particles.
  • the process of the present invention generally is limited, in temperature, to about 500°C as its upper limit.
  • Hydrogen partial pressure within a concentration range from a trace to about 70% by volume is generally cycled within a range of which 0.1 atmosphere absolute is the lower limit and 200 atmospheres hydrogen is the upper limit.
  • temperature of operation is a function of the inherent nature of the.hydridable material and the partial pressure of hydrogen in the feed gas.
  • the upper limit of 500°C is merely a rough guide, this temperature being usable only with all-metal pellets or those bound by heat resistant resins such as polytetrafluoroethylene.
  • hydride-forming metals including Mg, FeTi, CaNi . , LaNi 5 (and other AB 5 alloys).
  • the metallic hydride is an alloy of at least two elements from the group of iron, titanium nickel, calcium, manganese, magnesium and rare earth elements. Suitable materials are sold by MPD Technology Corp.
  • a front is established as defined by T 2 -T 1 where T2 is the maximum temperature of the bed, and T1 is the minimum temperature of the bed ahead of the front.
  • T2 is the maximum temperature of the bed
  • T1 is the minimum temperature of the bed ahead of the front.
  • the front as defined by T 2 -T 1 in °C will exceed about 40°C, and preferably 50°C and will have a length less than 10 feet and preferably less than 3.5 feet.
  • the ballast when combined in proper spatially distributed form, as described, permits the front to move at a rapid velocity of at least 0.1 ft./min., and preferably 0.35 ft./min. through the reactor.
  • the hydridable material After the front passes the length of the bed, the hydridable material has generally reached its absorption capacity and feed to the bed is terminated. Then the bed is desorbed by lowering the bed pressure. Generally this is to the starting point P 1 . Pressure reduction is controlled so that a uniform ( ⁇ 50%, and preferably ⁇ 20%) rate of hydrogen desorption is obtained from the hydridable material. This is determined empirically. The object of the desorption reaction is to proceed substantially along the line B"-A. If pressure reduction is too fast then subcooling occurs and the desorption rate slows. If pressure reduction is too slow then one is not utilizing the stored heat properly to effect rapid desorption.
  • the process of the present invention when carried out employing metal bonded composite hydride structures, e.g.
  • valves 10 and 12 ' are alternately opened and closed to permit a hydrogen-bearing feed stream into their respectively associated reactors 14 and 16.
  • valve 12 closed and valve 10 opened in the phase of operation illustrated, hydrogen-bearing feed stream passes through hydriding reactor 14 and hydrogen-depleted off-gas therefrom passes through open valve 18 either back through recirculation blower 20 (optional) or to hydrogen-depleted stream removal line 21. Gas from recirculation blower 20 is recycled, in combination with incoming hydrogen-bearing feed stream, for further hydrogen extraction.
  • valve 24 is closed and previously hydrided reactant in reactor 16 is permitted to degas by depressurization while evolved hydrogen passes through valve 22 to the recovered hydrogen stream.
  • valve 22 Upon completion of the hydriding reaction in reactor 14 and the dehydriding reaction in reactor 16, valve 22 is closed and reactor 16 is repressurized to P 2 . Valves 12 and 24 are then opened to permit beginning-of the hydriding reaction in the next cycle of reactor 16, while valves 10 and 18 are closed and valve 26 is opened to permit, upon depressurization of the reactant in reactor 14, dehydriding and passage of evolved hydrogen from reactor 14 to the recovered hydrogen stream.
  • typical temperatures to and from the hydriding reactor of 100°F (37°C) and 177°F (80°C) are indicated.
  • Such process temperatures would be within a normal range for a hydriding pressure of about 400-500 psia (about 27.2 to 34 atmospheres absolute) and a dehydriding pressure of about 20-50 psia (1.36 to 3.4 atmospheres absolute), for a hydrogen-bearing feed stream.
  • a composite pellet permitting absorption of 100% of the heat of reaction during absorption and assuming 100% absorption and utilization of that heat for desorption is designed assuming nickel powder (325 mesh) is combined with particulate lanthanum pentanickel (325 mesh).
  • the nickel powder has a particle size, i.e. within 50 ⁇ % of the particle size of the lanthanum pentanickel.
  • the design energy criteria for the composite are as follows:
  • the design pellet On the basis of 100 grams lanthanum pentanickel, the design pellet consists of 18.3% lanthanum pentanickel and 81.7% nickel. Although for energy purposes the quantity of a larger size nickel powder would remain the same, such large size particles may not necessarily give the heat transfer to achieve the desired short reaction front and fast reaction front velocity necessary to give commercially desirable cycling times.
  • the flow rate through an insulated tubular reactor packed with these composite pellets of one-half inch diameter, one-half inch in length must be regulated to maintain the design conditions. For example even though a composite is properly designed it is possible to "overpower" the composite by utilizing too fast a flow rate. The capacity of the composite may be under utilized by too slow a rate. For most cases, a reaction front length of 1-4 feet is used.
  • a series of hydrogen separations were made using a gas blend of 50% hydrogen and 50% methane (volume percent) as the feed for Runs 1-4.
  • the feed for subsequent runs was ammonia purge gas as described in Example I.
  • One type of composite pellets were formulated utilizing an initial composition consisting of 24.3% lanthanum pentanickel (325 mesh U.S. standard), 72.8% nickel powder (80 mesh U.S. Standard) and 2.9% of a silicone rubber, such percentages being by weight.
  • the pellets were fabricated by mixing the prescribed amounts of components and then forming composite, hydrogen permeable cylinders on a Carver press incorporating a standard KB R tablet dye. The cylinders produced were one-half inch in diameter and one-half inch in length, then diced.
  • the sintered LaNi 5 /Nickel ballasted pellets were prepared by mixing LaNi S (25%) and nickel powder sold under the trademark, Inco 123 and then pressing into pellets. The pellets were sintered at 1400°F for 30 minutes under flowing argon. After sintering the pellets were crushed and sieved to -4 to +10 mesh U.S. standard size. Other types of composites specified were prepared in a manner similar to this, in conventional manner or as in Example 1.
  • An insulated 5 foot, 3/4 inch tubular reactor having an ID of 0.68 inches was filled with approximately 1,000 grams of composite pellets.
  • the column was prepressurized with methane to 500 psia to minimize pressure surges during introduction of the feed. After prepressurization, the feed was introduced into the bottom of the column at 500 psia.
  • a frontal length was calculated by monitoring the exit gas from the reactor and dividing the time required from introduction of the feed to time it took for the hydrogen to break through the reactor by the superficial velocity of the feed gas. Table 1 shows the summary of several runs, and pellet forms using this feed gas.
  • the resin bonded systems performed well in view of the short reaction front L f obtained and high V fl e.g., above 0.4.
  • the polyethylene bonded system did the poorest and that may have been attributable to plugging of the pores.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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EP82105933A 1981-07-02 1982-07-02 Gewinnung von Wasserstoff aus Gasströmen mittels Metallhydriden Expired EP0069941B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/279,883 US4360505A (en) 1981-07-02 1981-07-02 Recovering hydrogen from gas stream using metal hydride
US279883 1981-07-02

Publications (2)

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EP0069941A1 true EP0069941A1 (de) 1983-01-19
EP0069941B1 EP0069941B1 (de) 1986-04-23

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US (1) US4360505A (de)
EP (1) EP0069941B1 (de)
CA (1) CA1181229A (de)
DE (1) DE3270745D1 (de)
ZA (1) ZA824636B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2159133A (en) * 1984-05-24 1985-11-27 Central Electr Generat Board Hydrogen absorber body
EP0315582A3 (en) * 1987-11-04 1989-12-06 Hwt Gesellschaft Fur Hydrid- Und Wasserstofftechnik Mbh Process and device for hydrogen purification
EP0355206A1 (de) * 1988-08-22 1990-02-28 Dsm N.V. Kontinuierliches Verfahren zur Trennung von hochreinem Wasserstoff aus einer Wasserstoff enthaltenden Gasmischung
EP0422559A1 (de) * 1989-10-09 1991-04-17 Matsushita Electric Industrial Co., Ltd. Verfahren zur Reinigung von Edelgasen
DE19534095A1 (de) * 1995-09-14 1997-03-27 Siemens Ag Verfahren und Vorrichtung zum Abscheiden von Wasserstoff aus einem Gasgemisch
DE102005004589A1 (de) * 2005-02-01 2006-08-10 Bayerische Motoren Werke Ag Druckerhöhungseinrichtung für Wasserstoff

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Publication number Priority date Publication date Assignee Title
DE3247361A1 (de) * 1982-12-22 1984-06-28 Studiengesellschaft Kohle mbH, 4330 Mülheim Verfahren zur abtrennung und reinigung von wasserstoff
US4749558A (en) * 1978-02-02 1988-06-07 Studiengesellschaft Kohle Mbh Method of separating and purifying hydrogen
US4687650A (en) * 1981-07-02 1987-08-18 Ergenics, Inc. Methods of extracting hydrogen from a gas
US4544527A (en) * 1982-10-25 1985-10-01 Ergenics, Inc. Hydrogen from ammonia
US4769225A (en) * 1983-12-08 1988-09-06 The United States Of America As Represented By The United States Department Of Energy System for exchange of hydrogen between liquid and solid phases
US4659554A (en) * 1984-06-04 1987-04-21 Allied Corporation Low-energy process for separation of hydrogen isotopes
US4696806A (en) * 1986-04-09 1987-09-29 Air Products And Chemicals, Inc. Metal hydride adsorption process for hydrogen purification
US4704267A (en) * 1986-05-21 1987-11-03 Air Products And Chemicals, Inc. Production of hydrogen from ammonia
DE3809680A1 (de) * 1988-03-17 1989-09-28 Mannesmann Ag Anlage zur verdichtung von wasserstoffgas
JPH0825721B2 (ja) * 1989-08-04 1996-03-13 キヤノン株式会社 水素貯蔵体及び該水素貯蔵体への水素貯蔵方法
US4971605A (en) * 1989-09-18 1990-11-20 Institute Of Gas Technology Isothermal thermo-cyclic processing
US5354040A (en) * 1991-11-28 1994-10-11 Mitsubishi Materials Corporation Apparatus for closed cycle hydrogenation recovery and rehydrogenation
US5296438A (en) * 1992-09-29 1994-03-22 The United States Of America As Represented By The United States Department Of Energy Dimensionally stable metallic hydride composition
US5917114A (en) * 1996-11-01 1999-06-29 The Ohio State University Degassing of liquid aluminum and other metals
WO2002008117A1 (en) * 2000-07-25 2002-01-31 Apollo Energy Systems, Incorporated Ammonia cracker for production of hydrogen
US6503298B1 (en) * 2001-04-30 2003-01-07 Battelle Memorial Institute Apparatus and methods for hydrogen separation/purification utilizing rapidly cycled thermal swing sorption
US6722154B1 (en) * 2003-05-09 2004-04-20 Energy Conversion Devices, Inc. Metal hydride based air cooling method and apparatus
US20050229489A1 (en) * 2004-04-19 2005-10-20 Texaco Inc. Apparatus and method for hydrogen generation
US8152898B2 (en) * 2008-10-24 2012-04-10 Praxair Technology, Inc. Helium recovery process
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DE3270745D1 (en) 1986-05-28
CA1181229A (en) 1985-01-22
ZA824636B (en) 1983-11-30
EP0069941B1 (de) 1986-04-23

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